某污染场地地下水中溶解性有机质组成特征及其自然衰减指示作用

赵萌; 姜永海; 贾永锋; 廉新颖; 尚长健; 臧永歌; 冯帆

doi:10.12153/j.issn.1674-991X.20220813

某污染场地地下水中溶解性有机质组成特征及其自然衰减指示作用

doi: 10.12153/j.issn.1674-991X.20220813

赵萌^{1, 2,},
姜永海^{1, 2},
贾永锋^{1, 2},
廉新颖^{1, 2},
尚长健^{1, 2},
臧永歌^{1, 2},
冯帆^{1, 2, 3, ,}

1.
环境基准与风险评估国家重点实验室，中国环境科学研究院
2.
国家环境保护地下水污染模拟与控制重点实验室, 中国环境科学研究院
3.
北京师范大学水科学研究院

基金项目: 国家重点研发计划项目(2019YFC1806204)；国家自然科学基金项目(41907178)

详细信息

作者简介:
赵萌(1997—)，女，硕士研究生，主要从事地下水污染与控制研究，zhmheng@163.com

通讯作者:
冯帆(1994—)，女，博士，主要从事地下水污染与控制研究，qbunny1634@163.com

中图分类号: X523
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- 被引次数: 0
出版历程
- 收稿日期: 2022-08-16
- 网络出版日期: 2023-09-20

Characterizing the composition of dissolved organic matter in groundwater at a polluted site and its indicating significance for natural attenuation

ZHAO Meng^{1, 2
,},
JIANG Yonghai^{1, 2},
JIA Yongfeng^{1, 2},
LIAN Xinying^{1, 2},
SHANG Changjian^{1, 2},
ZANG Yongge^{1, 2},
FENG Fan^{1, 2, 3
, ,}

1.
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences
2.
State Environmental Protection Key Laboratory of Simulation and Control of Groundwater Pollution, Chinese Research Academy of Environmental Sciences
3.
College of Water Sciences, Beijing Normal University

摘要

摘要:
溶解性有机质（DOM）影响着地下水中污染物的降解转化行为，其结构组成的变化可以反映外来污染物的迁移转化过程。以山东某污染场地地下水为研究对象，利用三维荧光光谱（EEM）、同步荧光光谱（SFS）和荧光区域体积积分法（FRI）分析研究区地下水DOM的组成及结构变化规律，并结合自然衰减能力评估方法——水文地球化学指标分析方法和微生物学分析方法探讨DOM光谱信息对地下水有机污染自然衰减效果的指示作用。结果表明：在地下水有机污染持续存在和长期的微生物作用下，地下水DOM中类腐殖质和类蛋白物质组分含量均增加，随着生物降解作用越来越强烈，DOM中类蛋白物质占比逐渐升高。基于FRI分区理论，提出可用特定荧光分区相对含量比〔P_(Ⅰ+Ⅱ)/P_Ⅴ〕，即类蛋白物质与类腐殖质物质的相对含量比，作为快速判断地下水有机污染自然衰减生物作用效果的代替表征指标，P_(Ⅰ+Ⅱ)/P_Ⅴ越大，表明自然衰减中的生物降解作用越强。
- 地下水 /
- 溶解性有机质（DOM） /
- 荧光特征 /
- 自然衰减
Abstract:
Dissolved organic matter (DOM) affects the degradation and transformation of pollutants in groundwater, and the changes of DOM structural composition can reflect the migration and transformation process of external pollutants. Taking groundwater from a polluted site in Shandong Province as the research object, three-dimensional fluorescence spectroscopy (EEM), synchronous fluorescence spectroscopy (SFS) and fluorescence region volume integral method (FRI) were used to analyze the composition and structure of the groundwater DOM. The role of DOM spectral information in indicating the natural attenuation effect of groundwater organic pollution was investigated in combination with the natural attenuation capacity assessment methods, i.e. hydrogeochemical index analysis method and microbiological analysis method. The results showed that the content of both humus-like and protein-like substances in groundwater increased under the persistence of organic pollution in groundwater and long-term microbial action, and the proportion of protein-like substances gradually increased with the increasingly strong biodegradation. Based on FRI region theory, a substitute characterization index was proposed to quickly assess the effect of the biodegradation in the natural attenuation of organic pollution in groundwater: the ratio of relative contents of specific fluorescence regions [P_{(Ⅰ +Ⅱ)}/P_Ⅴ], that was, the ratio of the relative content of protein-like substances to humus-like substances. The larger the value of P_(Ⅰ+Ⅱ)/P_Ⅴ was, the stronger the biodegradation in natural attenuation was.
- groundwater /
- dissolved organic matter (DOM) /
- fluorescence characteristics /
- natural attenuation

HTML全文

图 1 地下水流向及地下水监测井分布

Figure 1. Groundwater flow direction and locations of the groundwater wells

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图 2 各监测井地下水样同步荧光光谱

Figure 2. Synchronized fluorescence spectra of groundwater samples from various monitoring wells

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图 3 各监测井地下水样DOM红外光谱

Figure 3. FTIR spectra of DOM of groundwater samples from various monitoring wells

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图 4 各监测井地下水样三维荧光光谱

Figure 4. Three-dimensional fluorescence spectrum of groundwater samples from various monitoring wells

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图 5 各监测井地下水微生物代谢过程关键酶丰度

Figure 5. Abundance of major enzymes in the microbial metabolism process of groundwater in various monitoring wells

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表 1 各监测井地下水常规水质指标及特征污染物指标

Table 1. Statistical information on the groundwater conventional quality indicators and characteristic pollutant indicators in various monitoring wells

监测井	井深/m	pH	TDS/ (mg/L)	总硬度/ (mg/L, 以CaCO₃计)	耗氧量/ (mg/L)	石油烃(C₁₀~C₄₀) 浓度/(mg/L)	苯浓度 / (μg/L)	氯乙烯浓度 / (μg/L)	TOC 浓度/ (mg/L)
MW1	12	6.65	2 450	502	10.1	0.87	9 180	3 100	36.23
MW2	12	6.81	2 320	917	22.1	0.19	242	1 130	10.83
MW3	12	6.68	3 060	1 850	26.2	0.20	462	2 030	7.71
MW4	12	6.97	1 680	1 100	18.8	0.13	803	3 050	4.38

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表 2 已有研究中部分常见有机污染物及相关降解产物三维荧光光谱信息

Table 2. Three-dimensional fluorescence spectral information of some common organic pollutants and related products of degradation in previous researches

物质	Ex/Em	对应荧光峰
石油的主要成分	224/328^[24]	C₂
	232/346^[25]	C₂
	210/310^[25]	C₁
	220/305、230/340^[25]	C₂
石油的降解产物	236/350^[26]	C₂
石油的降解产物	220/290^[27]	C₁
苯	220/330^[23]	C₂
石油、苯系物和多环芳烃及其降解产物	237(288)/358.7^[28]	C₂
微生物降解作用有关的腐殖质	250/(410~460)^[23]	C₃
微生物降解作用有关的腐殖质	248/(390~460)^[24]	C₃
注：所有溶剂均为水。

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表 3 各监测井地下水的FI、BIX、HIX、β∶α指数描述统计

Table 3. Descriptive statistics of FI, BIX, HIX, (β∶α) of groundwater in various monitoring wells

监测井	FI	BIX	HIX	β∶α
MW1	1.82	1.18	1.14	1.08
MW2	1.80	1.17	2.87	1.07
MW3	1.82	1.22	3.30	1.10
MW4	1.84	1.14	3.43	1.04

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表 4 地下水DOM三维荧光光谱区域积分结果

Table 4. Volume integration results of DOM in different regions of three-dimensional fluorescence spectrum of groundwater

监测井	Ф_i/(10⁵ a.u.·nm²)					$\displaystyle\sum _{i=1}^{5}{\varPhi }_{i}$/(10⁵ a.u.·nm²)	P_i/%
监测井	Ⅰ	Ⅱ	Ⅲ	Ⅳ	Ⅴ	$\displaystyle\sum _{i=1}^{5}{\varPhi }_{i}$/(10⁵ a.u.·nm²)	Ⅰ	Ⅱ	Ⅲ	Ⅳ	Ⅴ
MW1	12.9	16.6	10.2	12.5	21.7	73.9	17.44	22.42	13.78	16.94	29.43
MW2	2.3	4.8	5.7	4.2	13.8	30.8	7.39	15.62	18.68	13.56	44.74
MW3	0.2	1.5	3.1	5.6	18.5	28.9	0.58	5.33	10.74	19.47	63.87
MW4	0.2	1.3	2.3	3.2	11.2	18.2	1.13	6.91	12.88	17.54	61.54

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表 5 各监测井地下水水化学指标

Table 5. Hydrochemistry indexes of groundwater in various monitoring wells

监测井	ORP/ mV	DO浓度/ (mg/L)	SO₄ ²⁻浓度/ (mg/L)	NO₃ ⁻浓度/ (mg/L)¹⁾	(P_Ⅰ+P_Ⅱ)/ P_Ⅴ
MW1	−52.6	3.01	191	0.9	1.35
MW2	−29.7	2.44	202	12.1	0.51
MW3	−26.0	1.54	166	10.7	0.09
MW4	−18.4	3.57	278	14.1	0.13
背景值			304	22.5
1) 以N计。

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